EP0367365A2 - Benzisothiazoles, process for their preparation and their use as pesticides - Google Patents

Abstract

Novel benzisothiazoles of the general formula I <IMAGE> in which X and R have the meaning indicated in the description, processes for their preparation and their use as pesticides, in particular against nematodes, are described.

Description

The invention relates to new benzoisothiazoles, their preparation and use as pesticides, in particular against nematodes.

3-Thio-5-nitro-benzisothiazoles are already known which have bacterial and strongly fungicidal properties (DE 3 202 298).

The object of the present invention was to provide pesticides with better properties.

worin
X Wasserstoff, Halogen, C₁₋₄-Alkyl, C₁₋₄-Alkylthio, C₁₋₄-Alkoxy, Di-C₁₋₄-­alkylamino, Halogen-C₁₋₄-alkyl, Halogen-C₁₋₄-alkoxy, Halogen-C₁₋₄-­alkylthio, C₃₋₆-cycloalkyl, Halogen-C₃₋₆-cycloalkyl, Halogen-C₃₋₆-­cycloalkylmethoxy, Halogen-C₃₋₆-Cycloalkylmethylthio, Nitro, Cyano, Amino, Phenyl, Halogenphenyl, Phenoxy, Phenylthio oder Halogenphenylthio und
R einen ein- oder mehrfach, gleich oder verschieden durch Halogen substi­tuierten C₁₋₁₂-Alkyl-, C₂₋₁₂-Alkenyl-, C₂₋₁₂-Alkinyl-, C₃₋₆-Cycloalkyl-­oder C₃₋₆-Cycloalkylmethylrest bedeuten,
eine überraschend gute nematizide Wirkung bei gleichzeitig guter Pflanzen­verträglichkeit zeigen.It has now been found that compounds of the general formula I

wherein
X is hydrogen, halogen, C₁₋₄-alkyl, C₁₋₄-alkylthio, C₁oxy-alkoxy, di-C₁₋₄-alkylamino, halogen-C₁₋₄-alkyl, halogen-C₁₋₄-alkoxy, halogen-C₁ ₋₄-alkylthio, C₃₋₆-cycloalkyl, halogen-C₃₋₆-cycloalkyl, halogen-C₃₋₆-cycloalkylmethoxy, halogen-C₃₋₆-cycloalkylmethylthio, nitro, cyano, amino, phenyl, halophenyl, phenoxy, phenylthio or halophenylthio and
R is a C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl, C₂₋₁₂-alkynyl, C₂₋₁₂-alkynyl, C₃₋₆-cycloalkyl or C₃₋₆-cycloalkylmethyl radical which is substituted one or more times, identically or differently, by halogen,
show a surprisingly good nematicidal effect with good plant tolerance.

Halogen is to be understood as Cl, F, Br and iodine.

The term haloalkyl, haloalkoxy, haloalkylthio, halocycloalkyl means that one or more hydrogen atoms of the alkyl or cycloalkyl radical have been replaced by halogen.

wobei X die in Formel I angegebene Bedeutung hat und A Wasserstoff, Ammonium oder ein Alkalimetall bedeutet, mit Verbindungen der Formel Z-R, wobei Z eine Fluchtgruppe wie z.B. Halogen, Mesylat und Tosylat ist und R die in Formel I angegebene Bedeutung hat, in einem inerten Lösungsmittel oder Lösungsmittelgemisch bei gebenenfalls erhöhter Temperatur und gegebe­nenfalls bei erhöhtem Druck in Gegenwart einer Base umsetzt.The compounds of the formula I according to the invention can be prepared by methods known per se in that compounds of the formula II

where X has the meaning given in formula I and A means hydrogen, ammonium or an alkali metal, with compounds of the formula ZR, where Z is an escape group such as halogen, mesylate and tosylate and R has the meaning given in formula I, in an inert Solvent or solvent mixture at an optionally elevated temperature and optionally at elevated pressure in the presence of a base.

Organic and inorganic bases can be used as bases, e.g. tertiary amines such as triethylamine and tripropylamine, alkali and alkaline earth metal hydrides, hydroxides, carbonates and bicarbonates, but also alkali metal alcoholates, such as z. Sodium methylate or potassium tert-butoxide.

Suitable solvents for the preparation of the compounds according to the invention are e.g. Diethyl ether, dioxane and tetrahydrofuran, aliphatic and aromatic hydrocarbons such as toluene and petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, carbon tetrachloride, chloroform; Nitriles such as acetonitrile, propionitrile; N, H-dialkylated amides such as dimethylformamide; Ketones such as acetone, methyl ethyl ketone: dimethyl sulfoxide, sulfolane and water and alcohols, e.g. Methanol, ethanol, isopropanol or butanol and the mixtures of such solvents with one another.

Depending on the reactants, the reaction is carried out at temperatures between -70.degree. C. and 120.degree. Depending on the reactants, the use of pressure can also be expedient. The then attached applied pressure is between 1 and 25 bar. The reaction time is approximately 0.5 to 48 hours. The reaction mixture is then poured onto ice / water, extracted and worked up in a manner known per se. The products obtained can be purified in the usual way by recrystallization, vacuum distillation or column chromatography.

The compounds of formula II used as starting material are either known or can be prepared by processes known per se.

Because of the nematicidal activity with good plant tolerance, the compounds according to the invention can be used successfully in crop protection as pesticides in agriculture, in viticulture, fruit growing and horticulture and in forest crops.

The plant parasitic nematodes which can be controlled according to the invention include, for example, the root gall nematodes, such as Meloidogyne incognita, Meloidogyne hapla, Meloidogyne javanica, the cyst-forming nematodes, such as Globodera rostochiensis, Heterodera schachtii, Heterodera avoderc, Holioderi, Heterioderi, Heterioderi, or Heteri - and foliar nematodes, such as Ditylenchus dipsaci, Ditylenchus destructor, Aphelenchoides ritzemabosi, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus and Tylenchorhynchus dubius, Tylenchorhynchus claytoni, Rotylenchus robustus, Heliocotylenchus multicinctus, Radopholus similis, Belonolaimus longicaudatus, Longidorus elongatus and Trichodorus primitivus.

Because of the insecticidal and acaricidal properties of the compounds according to the invention, they also offer possible uses both in the treatment against pests in the most varied stages of the crop plants and also against pests on humans and animals.

The active compounds according to the invention are used in the form of their commercially available formulations and / or use forms prepared from these formulations.

The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The application rate for controlling nematodes per hectare is about 0.03 kg to about 10 kg, preferably about 0.3 kg to about 6 kg.

The active ingredients or their mixtures can be converted into the usual formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic substances , Fine encapsulation in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc. as well as ULV cold and warm fog formulations.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents.

Suitable liquid solvents are essentially aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol, glycol and their ethers and esters , Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water.

Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and pressure, e.g. Aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

Natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers, and broken and fractionated natural rocks such as calcite, marble, pumice as solid carriers for granules , Sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks.

As emulsifiers or foam-generating agents, non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, aryl sulfonates and protein hydrolyzates.

As dispersants are e.g. Called lignin, sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can also be used in the formulations.

Dyes such as inorganic pigments, e.g. Iron dioxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo-metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc are also used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

• I. Spritzpulver
  10 Gewichtsteile der Verbindung gemäß Beispiel 1 werden mit 12 Ge­wichtsteilen Calciumsalz der Ligninsulfonsäure. 76 Gewichtsteilen Kaolin und 2 Gewichtsteilen Dialkylnaphthalinsulfonat innig vermischt und vermahlen.
• II. Stäubepulver
  2,5 Gewichtsteile der Verbindung gemäß Beispiel 1 werden in 10 Teilen Methylenchlorid gelöst und auf eine Mischung von 25 Gewichtsteilen pulverförmige Kieselsäure und 71,5 Gewichtsteilen Talkum sowie 1 Ge­wichtsteil Sudanrot gegeben. Das Lösungsmittel wird im Vakuum ent­fernt und der Rückstand fein vermahlen.
• III. Granulat
  5 Gewichtsteile der Verbindung gemäß Beispiel 1 werden in 10 Teilen Methylenchlorid gelöst und auf 95 Gewichtsteile granuliertes Atta­pulgit der Korngröße 0,3 - 0,8 mm aufgesprüht und getrocknet.
• IV. Emulsionskonzentrat 20 Gewichtsteile der Verbindung gemäß Beispiel 1 werden in einer Mischung aus 75 Gewichtsteilen Isophoron und 5 Gewichtsteilen eines Gemisches aus 30 Teilen Phenylsulfonat-Calciumsalz, 30 Teilen Rhizinus-Polyglycolat mit 40 Mol% Ethylenoxid und 40 Teilen eines Copolymeren von Propylen- und Ethylenoxid gelöst.

Examples of formulations are:

• I. wettable powder
  10 parts by weight of the compound according to Example 1 are mixed with 12 parts by weight of calcium salt of lignin sulfonic acid. 76 parts by weight of kaolin and 2 parts by weight of dialkylnaphthalenesulfonate are intimately mixed and ground.
• II. Dust powder
  2.5 parts by weight of the compound according to Example 1 are dissolved in 10 parts of methylene chloride and added to a mixture of 25 parts by weight of powdered silica and 71.5 parts by weight of talc and 1 part by weight of Sudan red. The solvent is removed in vacuo and the residue is finely ground.
• III. granules
  5 parts by weight of the compound according to Example 1 are dissolved in 10 parts of methylene chloride and sprayed onto 95 parts by weight of granulated attapulgite with a particle size of 0.3-0.8 mm and dried.
• IV. Emulsion concentrate 20 parts by weight of the compound according to Example 1 are in a mixture of 75 parts by weight of isophorone and 5 parts by weight of a mixture of 30 parts of phenyl sulfonate calcium salt, 30 parts of castor polyglycolate with 40 mol% of ethylene oxide and 40 parts of a copolymer of propylene and ethylene oxide solved.

The following examples describe the preparation of the compounds according to the invention.

example 1 3-difluoromethylthio-1,2-benzisothiazole

: 1,599124.1 g (0.02 mol) of 1,2-benzisothiazole-3-thiolate, potassium salt are suspended in 25 ml of dioxane and a solution of 5.6 g (0.10 mol) of potassium hydroxide in 9 ml of water is added. At a temperature of 60-70 ° C, a steady stream of chlorodifluoromethane is initiated for 30 minutes. The mixture is allowed to cool, poured onto 500 ml of ice water and extracted several times with ethyl acetate. The organic phase is dried over magnesium sulfate, filtered and concentrated. The remaining oil is chromatographed on silica gel (eluent hexane / diethyl ester 9: 1).
Yield: 1.0 g = ̂ 22.9% of theory
n $\genfrac{}{}{0ex}{}{\text{20th}}{\text{D}}$

: 1.59912

Example 2 3- (3,4,4-trifluoro-3-butenylthio) -1, 2-benzisothiazole

: 1,580082.05 9 (0.01 mol) 1,2-benzisothiazole-3-thiolate, potassium salt are suspended in 25 ml dimethylformamide. A solution of 2.3 (0.01 mol) of 4-bromo-1,1,2-trifluorobutene-1 in 10 ml of dimethylformamide is added dropwise at a temperature of 20 ° C. The mixture is stirred at room temperature for 2 hours. The reaction mixture is poured into 300 ml of ice water and extracted several times with ethyl acetate. The organic phase is dried over magnesium sulfate, filtered and concentrated. The remaining oil is chromatographed on silica gel (eluent hexane / diethyl ester 9: 1).
Yield: 0.60 g = ̂ 22% of theory
n $\genfrac{}{}{0ex}{}{\text{20th}}{\text{D}}$

: 1.58008

The following compounds of the formula I are prepared in an analogous manner:

The following application example shows the biological effect of the compounds according to the invention.

Example of use A Control of root-bile nematodes (Meloidogyne incognita)

10% powder formulations of active ingredients are mixed evenly with soil that is heavily contaminated with the test nematodes. Then you fill the treated soil in 0.5 liter clay bowls, sow cucumber seeds and cultivate in a greenhouse at a soil temperature of 25-27 ° C. After a culture period of 25-28 days, the cucumber roots are washed out, examined for nematode infestation (root galls) in a water bath and the effectiveness of the active ingredient is determined in% compared to the contaminated control. If the nematode infestation is completely avoided, the efficiency is set at 100%.

With a dose of 10 mg of active ingredient per liter of soil, a nematode attack by Meloidogyne incognita could be avoided completely (100%) by the compound according to Example 2.

Example of use B Effect of prophylactic feed treatment against the common bean spider mite (Tetranychus urticae Koch)

Round leaf disks with a diameter of 14 mm are punched out of developed primary leaves of the bush bean (Phaseolus vulgaris nanus Aschers.) And placed untreated or after immersion treatment with an aqueous preparation containing 0.1% of active substance on wet filter paper, with the underside of the leaf pointing upwards . After the samples thus treated had dried, six adult Tetranychus urticae females were placed on each Leaf disc set and kept for 3 days at 25 ° C and 16 h per day with light (four repetitions). Then the dead and living females are counted and removed. The laid eggs are also counted. After another seven days, the living larvae are counted. The overall effect according to Abbott is calculated with reference to the untreated control.

The compounds according to the invention according to Examples Nos. 2 and 5 showed an 80-100% overall effect.

Example of use C Effect of curative treatment against common spider mite eggs (Tetranychus urticae Koch)

Round leaf disks with a diameter of 14 mm are punched from developed primary leaves of the bush bean (Phaseolus vulgaris nanus Aschers.) And placed on wet filter paper with the top facing downwards. At least 5 adult Tetranychus urticae females are placed on each leaf disc and kept for 2 days at around 25 ° C, 50 - 60% relative humidity and 16 hours of light per day. After the adults have been collected, the leaf disks with the deposited eggs are immersed in a preparation containing 0.016% of active ingredient and wetting agent. As a control, leaf disks are immersed in water, the wetting agent being present in the same concentration as in the preparation containing the active ingredient. After the eggs have been counted, the leaf disks are kept at about 25 ° C., 50-60% relative atmospheric humidity and 16 hours of light per day for 7 days. The effect is calculated from the percentage difference between laid eggs and live larvae with reference to the Abbott control. The average is three repetitions.

The compound of the invention according to Example 4 showed an activity of 80% or more.

Example of use D Killing effect on eggs / larvae of the corn rootworm (Diabrotica undecimpunctata)

The compounds according to the invention are used as an aqueous preparation with an active compound concentration of 0.1%. 0.2 ml of these active ingredient preparations are pipetted onto the bottom of a polystyrene petri dish and onto the corn seedling contained therein and onto the approx. 50 eggs of the corn rootworm (Diabrotica undecimpunctata) located in the shell center. The closed trays are set up for 4 days at 25 ° C under long day conditions. The criterion for the effectiveness assessment is the killing of eggs or the freshly hatching larvae at the end of the experiment.

The compound according to Example 5 achieved an 80-100% effect.

Claims (5)

1. Compounds of the general formula I

wherein
X is hydrogen, halogen, C₁₋₄-alkyl, C₁₋₄-alkylthio, C₁oxy-alkoxy, di-C₁₋₄-alkylamino, halogen-C₁₋₄-alkyl, halogen-C₁₋₄-alkoxy, halogen-C₁ ₋₄-alkylthio, C₃₋₆-cycloalkyl, halogen-C₃₋₆-cycloalkyl, halogen-C₃₋₆-cycloalkylmethoxy, halogen-C₃₋₆-cycloalkylmethylthio, nitro, cyano, amino, phenyl, halophenyl, phenoxy, phenylthio or halophenylthio
and
R is a C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl, C₂₋₁₂-alkynyl, C₂₋₁₂-alkynyl, C₃₋₆-cycloalkyl or C₃₋₆-cycloalkylmethyl radical which is mono- or polysubstituted, identically or differently, by halogen. 2. A process for the preparation of compounds of formula I, characterized in that compounds of formula II

where X has the meaning given in formula I and A means hydrogen, ammonium or an alkali metal, with compounds of the formula ZR, where Z is an escape group such as halogen, mesylate and tosylate and R has the meaning given in formula I, in an inert Solvent or solvent mixture at an optionally elevated temperature and optionally at elevated pressure in the presence of a base. 3. Use of compounds according to claim 1 of formula I for controlling pests, in particular nematodes. 4. pesticide characterized by a content of at least one compound according to claim 1 of the formula I. 5. Pesticides according to claim 4 in a mixture with carriers and / or auxiliaries.